A new exhibition profiling some of Australia's most influential and high-achieving women is on show in Canberra.

First Ladies at the National Portrait Gallery maps the great achievements and milestones of Australian women over the past 100 years.

It features the portraits and stories of 21 women, many of whom achieved notable firsts and were considered ahead of their time.

Their endeavours span diverse fields including politics, the arts, sport, science and business.

Among the famous faces on display are Governor-General Quentin Bryce, aviatrix Nancy Bird Walton, athletes Louise Sauvage and Cathy Freeman, as well as the first Australian-born woman to be awarded a Nobel Prize, Elizabeth Blackburn.

These portraits feature alongside lesser-known women such as Marjorie Cotton, whose work led to a transformation of Australian public libraries, and Dame Nancy Buttfield, the first South Australian woman elected to Federal Parliament.

The exhibition also showcases a variety of portraiture mediums, including painting, drawing, sculpture and photography and represents each of the decades between 1913 and 2013.

First Ladies will be on show at the National Portrait Gallery until June 16.